The electronic energy levels of some representative isolated and oxide-supported organic dyes, relevant for photovoltaic applications, are investigated using many-body perturbation theory within the GW approximation. We consider a set of all-organic dyes (denominated L0, L2, L3, and L4) featuring the same donor and anchor groups and differing for the linker moieties. We first calculate the energy levels of the isolated molecules, thus allowing us to address the effects of the different linker groups, and resulting in good agreement with photo-electron spectroscopic and electrochemical data. We then consider the L0 dye adsorbed on the (101) surface of anatase-TiO2. We find a density of occupied states in agreement with experimental photo-electron data. The HOMO-LUMO energy gap of the L0 dye is found to be reduced by ∼1 eV upon adsorption. Our results validate the reliability of GW calculations for photovoltaic applications and point to their potential as a powerful tool for the screening and rational design of new components of electrochemical solar cells.
REFERENCES
1.
B.
O'Regan
and M.
Grätzel
, Nature (London)
353
, 737
(1991
).2.
M.
Hahlin
, M,
Odelius
, M.
Magnuson
, E. M. J.
Johansson
, S.
Plogmaker
, D. P.
Hagberg
, L.
Sun
, and H.
Rensmo
, Phys. Chem. Chem. Phys.
13
, 3534
(2011
).3.
P.
Hohenberg
and W.
Kohn
, Phys. Rev.
136
, B864
(1964
).4.
W.
Kohn
and L. J.
Sham
, Phys. Rev.
140
, A1133
(1965
).5.
G.
Onida
, L.
Reining
, and A.
Rubio
, Rev. Mod. Phys.
74
, 601
(2002
).6.
L.
Hedin
, Phys. Rev.
139
, A796
(1965
).7.
M. S.
Hybertsen
and S. G.
Louie
, Phys. Rev. B
34
, 5390
(1986
).8.
E.
Salpeter
and H.
Bethe
, Phys. Rev.
84
, 1232
(1951
).9.
M.
Rohlfing
and S. G.
Louie
, Phys. Rev. B
62
, 4927
(2000
).10.
N.
Marom
, J. E.
Moussa
, X.
Ren
, A.
Tkatchenko
, and J. R.
Chelikowsky
, Phys. Rev. B
84
, 245115
(2011
).11.
C.
Faber
, I.
Duchemin
, T.
Deutsch
, and X.
Blase
, Phys. Rev. B
86
, 155315
(2012
).12.
C. E.
Patrick
and F.
Giustino
, Phys. Rev. Lett.
109
, 116801
(2012
).13.
D. P.
Hagberg
, J.-H.
Yum
, H.
Lee
, F.
De Angelis
, T.
Marinado
, K. M.
Karlsson
, R.
Humphry-Baker
, L.
Sun
, A.
Hagfeldt
, M.
Grätzel
, and Md. K.
Nazeeruddin
, J. Am. Chem. Soc.
130
, 6259
(2008
).14.
P.
Umari
, G.
Stenuit
, and S.
Baroni
, Phys. Rev. B
79
, 201104
(R) (2009
).15.
P.
Umari
, G.
Stenuit
, and S.
Baroni
, Phys. Rev. B
81
, 115104
(2010
).16.
E. M.
Johansson
, T.
Edvinsson
, M.
Odelius
, D. P.
Hagberg
, L.
Sun
, A.
Hagfeldt
, H.
Siegbahn
, and H.
Rensmo
, J. Phys. Chem. C
111
, 8580
(2007
).17.
M.
Pastore
and F.
De Angelis
, Phys. Chem. Chem. Phys.
14
, 920
(2012
).18.
M.
Pastore
, S.
Fantacci
, and F.
De Angelis
, J. Phys. Chem. C
114
, 22742
(2010
).19.
A. D.
Becke
, Phys. Rev. A
38
, 3098
(1988
);C.
Lee
, W.
Yang
, and R. G.
Parr
, Phys. Rev. B
37
, 785
(1988
).20.
T.
Körzdörfer
and N.
Marom
, Phys. Rev. B
86
, 041110
(R) (2012
).21.
F.
Bruneval
and M. M.
Marques
, J. Chem. Theory Comput.
9
, 324
(2013
).22.
The GWL code can be downloaded from the www.gwl-code.org website.
23.
P.
Giannozzi
et al., J. Phys. Condens. Matter
21
, 395502
(2009
).24.
M. M.
Rieger
, L.
Steinbeck
, I. D.
White
, H. N.
Rojas
, and R. W.
Godby
, Comput. Phys. Commun.
117
, 211
(1999
).25.
W.
Kang
and M. S.
Hybertsen
, Phys. Rev. B
82
, 085203
(2010
).26.
C.
Friedrich
, M. C.
Müller
, and S.
Blügel
, Phys. Rev. B
83
, 081101
(R) (2011
).27.
M.
Stankovski
, G.
Antonius
, D.
Waroquiers
, A.
Miglio
, H.
Dixit
, K.
Sankaran
, M.
Giantomassi
, X.
Gonze
, M.
Côté
, and. G.-M.
Rignanese
, Phys. Rev. B
84
, 241201
(R) (2011
).28.
We use the following pseudopotentials: C.blyp-mt.UPF for the C atom, H.blyp-vbc.UPF for H, O.blyp-mt.UPF for O, S.blyp-mt.UPF for S, and N.blyp-mt.UPF for N.
29.
P.
Umari
and S.
Fabris
, J. Chem. Phys.
136
, 174310
(2012
).30.
G.
Stenuit
, C.
Castellarin-Cudia
, O.
Plekan
, V.
Feyer
, K. C.
Prince
, A.
Goldoni
, and P.
Umari
, Phys. Chem. Chem. Phys.
12
, 10812
–10817
(2010
).31.
C.
Faber
, C.
Attaccalite
, V.
Olevano
, E.
Runge
, and X.
Blase
, Phys. Rev. B
83
, 115123
(2011
).32.
F.
Caruso
, P.
Rinke
, X.
Ren
, M.
Scheffler
, and A.
Rubio
, Phys. Rev. B
86
, 081102
(R) (2012
).33.
M.
Palummo
, C.
Hoga
, F.
Sottile
, P.
Bagalá
, and A.
Rubio
, J. Chem. Phys.
131
, 084102
(2009
).34.
F.
Bruneval
, Phys. Rev. Lett.
103
, 176403
(2009
).35.
M. L.
Tiago
and J. R.
Chelikowsky
, Phys. Rev. B
73
, 205334
(2006
).36.
J. C.
Grossman
, M.
Rohlfing
, L.
Mitas
, S. G.
Louie
, and M. L.
Cohen
, Phys. Rev. Lett.
86
, 472
(2001
).37.
T.
Marinado
, D. P.
Hagberg
, M.
Hedlund
, T.
Edvinsson
, E. M. J.
Johansson
, G.
Boschloo
, H.
Rensmo
, T.
Brinck
, L.
Sun
, and A.
Hagfeldt
, Phys. Chem. Chem. Phys.
11
, 133
(2009
).38.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, Phys. Rev. Lett.
77
, 3865
(1996
).39.
D. P.
Hagberg
, T.
Marinado
, K. M.
Karlsson
, K.
Nonomura
, P.
Qin
, G.
Boschloo
, T.
Brinck
, A.
Hagfeldt
, and L.
Sun
, J. Org. Chem.
72
, 9550
(2007
).40.
C.
Anselmi
, E.
Mosconi
, M.
Pastore
, E.
Ronca
, and F.
De Angelis
, Phys. Chem. Chem. Phys.
14
, 15963
(2012
).41.
L.
Chiodo
, J. M.
García-Lastra
, A.
Iacomino
, S.
Ossicini
, J.
Zhao
, H.
Petek
, and A.
Rubio
, Phys. Rev. B
82
, 045207
(2010
).42.
M.
Landmann
, E.
Rauls
, and W. G.
Schmidt
, J. Phys. Condens. Matter
24
, 195503
(2012
).43.
Y. R.
Park
and K. J.
Kim
, Thin Solid Films
484
, 34
(2005
).44.
Y.
Ping
, D.
Rocca
, and G.
Galli
, Chem. Soc. Rev.
42
, 2437
(2013
).45.
C.
Freysoldt
, P.
Eggert
, P.
Rinke
, A.
Schindlmayr
, and M.
Scheffler
, Phys. Rev. B
77
, 235428
(2008
).46.
K. D.
Schierbaum
, S.
Fischer
, M. C.
Torquemada
, J. L.
de Segovia
, E.
Román
, and J. A.
Martín-Gago
, Surf. Sci.
345
, 261
(1996
).47.
G.
Xiong
, R.
Shao
, T.
Droubay
, A.
Joly
, K.
Beck
, S.
Chambers
, and W.
Hess
, Adv. Funct. Mater.
17
, 2133
(2007
).48.
In this case, we set the atomic positions of the isolated L0 dye in order to match those of the adsorbed one.
49.
J. B.
Neaton
, M. S.
Hybertsen
, and S. G.
Louie
, Phys. Rev. Lett.
97
, 216405
(2006
).50.
J. P.
Muscat
and D. M.
Newns
, Prog. Surf. Sci.
9
, 1
(1978
).51.
P.
Persson
, M. J.
Lundqvist
, R.
Ernstorfer
, W. A.
Goddard
, and F.
Willig
, J. Chem. Theory Comput.
2
, 441
(2006
).52.
C.
Cohen-Tannoudji
, B.
Diu
, and F.
Laloe
, Quantum Mechanics
(John Wiley & Sons
, Paris
, 1977
), Vol. 2
.53.
N.
Martsinovich
and A.
Troisi
, J. Phys. Chem. C
115
, 11781
(2011
).54.
M. J.
Lundqvist
, M.
Nilsing
, P.
Persson
, and S.
Lunell
, Int. J. Quantum Chem.
106
, 3214
–3234
(2006
).© 2013 AIP Publishing LLC.
2013
AIP Publishing LLC
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